CN103199201B - By the ito film of nitrogen plasma treatment and the organic electroluminescent device using this ito film - Google Patents

By the ito film of nitrogen plasma treatment and the organic electroluminescent device using this ito film Download PDF

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CN103199201B
CN103199201B CN201310078245.1A CN201310078245A CN103199201B CN 103199201 B CN103199201 B CN 103199201B CN 201310078245 A CN201310078245 A CN 201310078245A CN 103199201 B CN103199201 B CN 103199201B
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nitrogen
ito
electroluminescent device
organic electroluminescent
layer
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CN103199201A (en
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孙世焕
姜旼秀
全相映
金钟杰
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LG Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
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Abstract

The invention discloses a kind of tin indium oxide (ITO) film, wherein by nitrogen with selected from the nitrogen-containing compound including at least one atomic reaction of group of ITO constitution element In, Sn and O atom and prepare, or being present on the surface of ito film containing nitrogen compound of precipitation；The invention also discloses a kind of method preparing ito film, the method includes the step using the surface of nitrogen plasma treatment ito film。Ito film provided by the invention is used to demonstrate low-voltage, high efficiency and long-life as the organic electroluminescent device of anode。

Description

By the ito film of nitrogen plasma treatment and the organic electroluminescent device using this ito film
Related application
The application is the divisional application of No. 200480011315.0 application for a patent for invention (international application no PCT/KR2004/001181) being entitled as " by the ito film of nitrogen plasma treatment and the organic electroluminescent device using this ito film " submitted to China national Department of Intellectual Property on May 19th, 2004。
Technical field
The present invention relates to a kind of ito film using nitrogen plasma treatment and preparation method thereof, and a kind of use this ito film as the organic electroluminescent device of anode。
Background technology
Recently, owing to developing a kind of organic electroluminescent device using poly-(to phenylene vinylidene) (PPV) for conjugated polymer, therefore, the organic substance of such as conductive conjugated polymer has been carried out positive research。It addition, the research being devoted to be applied to this organic substance thin film transistor (TFT), sensor, laser instrument, optoelectronic device etc. and particularly organic electroluminescent device is constantly in progress。
Usually, organic electroluminescent device includes multiple structure, and the thin film being wherein made up of different organic substances is placed between two antielectrodes, in order to increase efficiency and the stability of equipment。As it is shown in figure 1, the most typical multiple structure of organic electroluminescent device include hole from anode 2 be injected into hole injection layer 3 therein, for transporting holes hole transmission layer 4, wherein complete emission layer 5 and the negative electrode 7 that hole and electronics combine。In order to improve device efficiency and life-span, this organic electroluminescent device may utilize the described multilamellar being made up of compounding substances or farther includes additional layer。It addition, for the manufacture simplifying equipment, the multifunctional material number of plies to comprise in minimizing equipment can be used。
Simultaneously, an electrode on substrate uses the transparent material having visible ray low absorptivity, the light launched from organic electroluminescent device is dispersed into outside, wherein tin indium oxide (ITO) is often used as transparent electrode material and anode for hole injection。
Organic electroluminescent device is according to following mechanism work。By hole injection layer/hole transmission layer and electron injecting layer, respectively by there is the anode of high work function and there is hole that the negative electrode of low work function produces and electronics is injected in emission layer, thus in emission layer, produce exciton。Finally, when exciton decays, launch corresponding to the light about energy。
The research of organic electroluminescent device has been directed generally to the color of the efficiency of equipment, life-span, driving voltage and light。Especially, between electroluminescent organic material and electrode, the electric charge on interface injects major effect efficiency and life-span。Therefore, the further investigation for improving interfacial characteristics has been made。
More particularly, the ITO surface treatment method being used for improving interfacial characteristics between ITO surface and hole injection layer is known。Routinely, ITO surface treatment method includes the cleaning by supersound process and/or UV ozone, Cement Composite Treated by Plasma etc.。In the middle of them, oxygen gas plasma processes the efficiency and the life-span that improve organic electroluminescent device。Referring to C.C.Wu et al., AppliedPhysicsLetter, 70,1348,1997。It is reported that the oxygen gas plasma on ITO surface processes the work function making ITO and sheet resistance increases, and make ITO surface more uniform。Referring to S.Fujita et al., JapaneseJournalofAppliedPhysics, 36,350,1997 and J.S.Kim et al., JournalofAppliedPhysics, 84,6859,1995。It addition, the oxygen gas plasma of ITO is processed the work function by increase ITO and improves hole and inject。Additionally, use the process of oxygen gas plasma can remove the polluter occurred on ITO surface, thus improve the performance of organic electroluminescent device。
It addition, the general interface ining contrast between organic material, the interface between inorganic oxide and ITO electrode and organic hole implanted layer has relatively unstable structure。In order to solve this problem, as in figure 2 it is shown, hole tunnel layer (tunnel, hole (buffering) layer) can be inserted between ITO and hole injection layer, in order to improve the adhesion that organic layer injects with hole。
Summary of the invention
It has been found that when using nitrogen plasma to replace oxygen plasma to process ITO surface, although the work function on ITO surface reduces, but, ITO surface is formed the thin film of nitrogen-containing compound, thus it ining contrast to the organic electroluminescent device of ito anode using oxygen plasma to process, the organic electroluminescent device being used in having on ITO surface the ito anode of the thin film of nitrogen-containing compound demonstrates the light efficiency of improvement, driving voltage and life-span。The present invention is based on this and finds。
A technical scheme according to the present invention, a kind of ito film is provided, the nitrogen-containing compound wherein prepared by nitrogen and at least one element reaction selected from tin indium oxide (ITO) component and the group of In, Sn and O, or the nitrogen-containing compound of deposition is present on the surface of ITO。
Another technical scheme according to the present invention, it is provided that a kind of method preparing ito film, the method includes the step on the surface of the film using nitrogen plasma treatment to comprise ITO。
Another technical scheme according to the present invention, it is provided that a kind of organic electroluminescent device including substrate, anode, emission layer and negative electrode, its Anodic includes the ito film of the present invention。
Will details are as follows to the present invention。
ITO is transparent conductive oxide, and the advantage with the high grade of transparency, low sheet resistance and good pattern Forming ability。By the strong point of these advantages, ITO is not only applicable to organic electroluminescent device, and is applied to include the electrode material in the various fields of liquid crystal display (LCD), solaode, plasma display and electronic paper (e-paper)。It addition, it is applied to the electromagnetic technology of protection cathode ray tube display and is applied to ITO ink。
Meanwhile, the feature as the ITO of anode for organic electroluminescent device is as follows。
ITO is the n-type Indium sesquioxide. of a kind of doped tin in large quantities。Indium sesquioxide. is a kind of quasiconductor, and wherein, the 2p track of oxonium ion forms valence band, and the 5s track of indium forms conduction band。Usually, along with ITO reverts to a certain degree, the Sn ion of oxonium ion and doping is as donor。It addition, along with the increase of these ion concentrations, fermi level is positioned on conduction band, thus ITO shows metallicity。
It is known that usually, ITO has higher than Sn concentration therein following content in its surface；Therefore fermi level increase and ITO have low work function；When ITO surface uses oxygen plasma to process, there is the surface of high Sn concentration and be corroded and oxygen is provided to surface, thus add the oxygen concentration on surface；Therefore, oxygen plasma processes and adds work function, thus the potential barrier that hole is injected can be reduced, and can improve the performance of organic electroluminescent device。
But, when oxygen atom spread and be incorporated into organic electroluminescent device such as hole injection layer organic layer in time, organic substance can be oxidized, thus loses the characteristic as hole injection layer。
We recognize that the ITO of the anode as organic electroluminescent device is likely to cause oxygen to be diffused into the problem in organic layer first, and use oxygen plasma that the process of ito anode is added the concentration of oxygen, and oxygen therefore can be caused to be diffused into the problem in organic layer。Therefore, in order to solve this problem, it is characterised by that it includes comprising the surface of the nitrogen-containing compound obtained by nitrogen plasma treatment according to the ito film of the present invention。
When ITO surface uses nitrogen plasma treatment, some nitrogen moleculars as plasma discharge gas (dischargegas) can be ionized under plasma conditions, then reacts to form nitrogen-containing compound with In, Sn of being present on ITO surface and O atom。Additionally, some nitrogen-containing compounds formed in the plasma can be deposited on the surface of ITO。
By for using the XPS analysis on the ITO surface of nitrogen plasma treatment can be seen that, it was observed that such as the nitrogen-containing compound of InN。
The nitrogen-containing compound formed on ITO surface can reduce the oxygen concentration on ITO surface, and the thin film of nitrogen-containing compound can stop oxygen atom to be dispersed into hole injection layer by ITO surface, thus improve hole and inject tunnel, hole (buffering) layer with interfacial adhesion such as organic electroluminescent device。Accordingly, because the above-mentioned functions of the nitrogen-containing compound on ITO surface, the performance of organic electroluminescent device can be improved。
It addition, nitrogen plasma reduces Sn concentration by surface corrosion, therefore can stablize the ITO interface of organic electroluminescent device, and life-span and the efficiency of equipment can be improved。
The available nitrogen of the nitrogen plasma that the present invention uses, or the mixing gas of nitrogen, oxygen, argon, hydrogen etc. is as plasma discharge gas。It addition, ammonia or include the mixing gas of ammonia nitrogen can be replaced to be utilized as plasma discharge gas。
On ITO surface, the concentration of oxygen can by using the hydrogen, ammonia or the oxygen that are combined with nitrogen or ammonia to be conditioned as plasma discharge gas。When argon, surface corrosion ratio is good。Therefore, containing these components mixing gas can be utilized to regulate ITO surface uniformity and on ITO surface the concentration of oxygen。
When active gases, more particularly there is the amount less than 3% of the highly active hydrogen gas to oxygen and mix with nitrogen, or ammonia is when mixing with nitrogen, it is present in the oxygen atom on ITO surface to react with hydrogen atoms, namely oxygen atom is reduced, so that surface becomes anaerobic condition, be conducive to formation nitrogen-containing compound on ITO surface。
Nitrogen plasma treatment carries out as follows, but is not limited to this。
After ito glass is incorporated in RF plasma reactor, by using turbine vacuum pump to apply 1 × 10-6The vacuum of the vacuum level of torr, then uses the nitrogen mass flow controllers (MFC) of 100sccm, and nitrogen flows into RF plasma reactor to maintain the vacuum level 10 minutes of 14mtorr with 63sccm。Use RF electromotor and RF controller that RF output is set, to produce nitrogen plasma。The variable of plasma process conditions includes vacuum level, RF power and process time。And, vacuum level can use nitrogen MFC to control, and RF power and process time can use RF controller to control。
Can be used for the preferred 30W～150W of scope of the nitrogen plasma power of the present invention。If RF power reduces, then it is hardly formed the thin film of nitrogen-containing compound。On the other hand, if RF power is more than 150W, then ITO surface corrosion increases, and surface uniformity reduces, and the thickness of nitrogen containing compound layer increases, thus hole tunnel-effect is highly difficult。
As long as the layer formed by nitrogen plasma treatment stops the diffusion of oxygen atom, idea of the invention also can be applied to the general conductor metal oxide for anode except ITO, and this is intended to be included within the scope of the present invention。Such as, conductor metal oxide includes indium zinc oxide (IZO)。
Accompanying drawing explanation
Fig. 1 is the sectional view with the conventional organic electroluminescent device including substrate/anode/hole injection layer/hole transmission layer/emission layer/electron transfer layer/cathode construction。
Fig. 2 is the sectional view with the conventional organic electroluminescent device including substrate/anode/hole tunnel layer (cushion)/hole injection layer/hole transmission layer/emission layer/electron transfer layer/cathode construction,
Wherein accompanying drawing labelling 1 represents substrate, accompanying drawing labelling 2 represents anode, accompanying drawing labelling 3 represents hole injection layer, accompanying drawing labelling 4 represents hole transmission layer, accompanying drawing labelling 5 represents emission layer, accompanying drawing labelling 6 represents that electron transfer layer, accompanying drawing labelling 7 represent negative electrode, and accompanying drawing labelling 10 represents hole tunnel layer (cushion)。
Fig. 3 shows the figure according to the organic electroluminescent device of preferred embodiment of the invention intensity of brightness in time。
Fig. 4 is the figure showing the organic electroluminescent device according to the preferred embodiment of the invention with the light efficiency of electric current density。
Fig. 5 is the XPS(X ray photoelectron spectroscopy on the ITO surface by using oxygen, argon-oxygen and nitrogen plasma treatment) figure that obtains。
Fig. 6 is the detailed view by using the XPS on ITO surface of the nitrogen plasma treatment figure obtained。
Detailed description of the invention
It is described in detail according to the preferred embodiments of the invention。The following examples are merely illustrative, and the scope of the present invention is not limited to this。
[embodiment 1]
The preparation (anode) of ito transparent electrode
Ito thin film coating will be usedThe glass substrate (fiber crops grain 7059 glass) of thickness is incorporated in the distilled water wherein dissolving dispersant, then supersound process。Dispersant for supersound process is a kind of product that can be obtained by FisherCompany, and uses with the distilled water of the frit twice purchased from MilliporeCompany。After washing ITO30 minute, distilled water is used to repeat supersound process twice, 10 minutes。After using distilled water to clean, carry out the supersound process of substrate as solvent continuously with isopropanol, acetone and methanol, then drying substrates。
Then, transfer substrates into plasma reactor, the pressure of 14mtoor, under 50W, use nitrogen plasma treatment 5 minutes, be then transferred into vacuum deposition apparatus。
The formation of hole (buffering) layer
The compound represented by following formula 1e is deposited on ito transparent electrode prepared as described above by thermal vacuum and depositsThickness, thus formed tunnel, hole (buffering) layer:
[formula 1e]
The formation of hole injection layer
The compound six azepine benzophenanthrene six nitrile (hexaazatriphenylenehexacarbonitrile) represented by following formula 1a is deposited on tunnel, hole (buffering) layer by thermal vacuum and depositsThickness to form hole injection layer:
[formula 1a]
The formation of hole transmission layer
The compound N PB represented by following formula 1c is deposited on hole injection layer by thermal vacuum and depositsThickness to form hole transmission layer:
[formula 1c]
The formation of emission layer
The compound Alq3 represented by following formula 1b is deposited on hole transmission layer by thermal vacuum and depositsThickness to form emission layer:
[formula 1b]
The formation of electron transfer layer
The compound represented by following formula 1d, for the material of electron transfer layer, by depositing on the emitterThickness to complete the formation of organic material film:
[formula 1d]
The formation of negative electrode
The lithium fluoride (LiF) of thickness andThe aluminum of thickness is sequentially depositing on the electron transport layer to form negative electrode, thus is provided with organic el device。
In the above-mentioned methods, the sedimentation rate of organic substance maintainsThe sedimentation rate of the lithium fluoride and aluminum that are used in negative electrode is respectively maintained atWithIn vacuum deposition process, vacuum level maintains 2 × 10-7～5 × 10-7torr。
[comparative example 1,2,3 and 4]
Except not carrying out nitrogen plasma treatment as described in Example 1 in comparative example 1, and comparative example 2,3 and 4 use respectively using the plasma of oxygen discharge gas as, using the argon of 2:1 ratio mixing and the gaseous mixture of oxygen as the plasma of discharge gas, replace outside nitrogen plasma using argon as the plasma of discharge gas, repeat embodiment 1 to obtain ito anode and organic electroluminescent device。
[test example]
The light efficiency of each organic electroluminescent device obtained by embodiment 1 and comparative example 2～4, driving voltage and life-span contrast, and result is as shown in table 1。
By under the room temperature of 25 DEG C, there is 100mA/cm2The electric current of electric current density there is the brightness (cd/m of the lower per unit area measuring organic electroluminescent device2), and by obtained value divided by electric current density, thus defining light efficiency, it represents with cd/A unit。
Driving voltage represents have 10mA/cm2The electric current of electric current density there is the voltage applied between two electrode terminals of lower organic electroluminescent device。
Life-span represents under the room temperature of 25 DEG C, has 100mA/cm2Electric current density electric current exist, lower organic electroluminescent device show 50% original intensity time time。
[table 1]
As shown in table 1, ining contrast to the comparative example 2 and 3 of the argon-oxygen plasma using oxygen gas plasma and mixing respectively, using the embodiment 1 on nitrogen plasma treatment ITO surface to demonstrate increases the light efficiency of about 25% and 10%, the driving voltage of reduction about 15% and 10% and increases by the life-span of 1000% and 250%。
Therefore, it in contrast to and use the organic electroluminescent device with oxygen gas plasma or the anode of argon-oxygen Cement Composite Treated by Plasma, when nitrogen plasma treatment ito anode is for time in organic electroluminescent device, it is provided that a kind of organic electroluminescent device with high light efficiency, low voltage and longer life is possible。
Fig. 3 is that figure, the Fig. 4 in life-span of display organic electroluminescence light emitting equipment is the figure of light efficiency being shown in organic electroluminescent device when using different types of plasma with electric current density when using different types of plasma。
Fig. 5 is the XPS figure on the ITO surface using oxygen, argon-oxygen and nitrogen plasma treatment。Fig. 6 is the detailed view by using the XPS on ITO surface of the nitrogen plasma treatment view obtained。As shown in Figure 6, observing two nitride peaks corresponding to InN within the scope of the bond energy of 397eV～400eV, nitrite peak is observed at the bond energy place of 404eV。
Work function and the atom of the ITO in each ito anode obtained by embodiment 1 and comparative example 1～4 form as shown in table 2。
[table 2]
Can be seen that from Fig. 5, Fig. 6 and Biao 2, from using the surface observation of the nitrogen plasma treatment nitrogen-atoms to about 13.3%, its amount corresponding to about 27% oxygen atom。
As can be seen from Table 2, based on the work function using the oxygenous gas comparative example 2 and 3 as the plasma of discharge gas to demonstrate increase。It addition, as shown in the result of XPS analysis, use the ITO surface that oxygen gas plasma processes to have the Sn concentration of reduction and the oxygen concentration of increase, thus add work function。
As shown in table 2, even if using the ITO surface in the embodiment 1 of nitrogen plasma to have the oxygen concentration of reduction and the work function of reduction, but as shown in table 1, ining contrast to comparative example 2 and 3, it demonstrates the life-span of the light efficiency of increase, the driving voltage of reduction and growth。
Therefore, from Fig. 5, Fig. 6 and Biao 2 is it will be apparent that some are used as being ionized under plasma condition containing nitrogen molecular of plasma discharge gas, then react with In, Sn of being present on ITO surface and O atom, to be formed containing nitrogen compound on ITO surface, or these nitrogenous molecule depositions are on ITO surface, and these nitrogen-containing compounds or nitrogen-atoms can work to improving above-mentioned performance。
Industrial applicibility
Known from the discussion above, the organic electroluminescent device of the ito anode with nitrogen plasma surface treatment used according to the invention stabilizes hole injection layer or the interfacial characteristics of tunnel, hole (buffering) layer by forming nitrogen-containing compound on the anode surface or nitrogen-atoms, thus improving life-span and the efficiency of this equipment, and this equipment can be driven at lower voltages。
Although the present invention is according to it is now recognized that most practical and preferred embodiment is described, it is to be expressly understood, however, that the present invention is not limited to disclosed preferred embodiment and accompanying drawing, otherwise, it is intended to cover the various modifications and variations in the spirit and scope of claims。

Claims (3)

1. the method preparing organic electroluminescent device, described organic electroluminescent device includes substrate, anode, hole injection layer, emission layer and negative electrode, and wherein, anode includes indium oxide tin film；
The method comprises the following steps: use nitrogen plasma treatment indium oxide tin film, make the nitrogen-containing compound prepared by nitrogen and at least one element reaction selected from tin indium oxide component and In, Sn and O, or the nitrogen-containing compound of deposition is present on the surface of indium oxide tin film；And
Indium oxide tin film forms the layer comprising six azepine benzophenanthrene six nitriles as hole injection layer。
2. the method preparing organic electroluminescent device according to claim 1, wherein, the discharge gas that described nitrogen plasma uses comprises nitrogen；Ammonia；Or the mixing gas of nitrogen and ammonia。
3. the method preparing organic electroluminescent device according to claim 1, wherein, the discharge gas that described nitrogen plasma uses comprises the mixing gas of at least one gas in nitrogen and ammonia and at least one gas in oxygen, argon and hydrogen。
CN201310078245.1A 2003-05-23 2004-05-19 By the ito film of nitrogen plasma treatment and the organic electroluminescent device using this ito film Expired - Lifetime CN103199201B (en)

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KR1020030032864A KR100808790B1 (en) 2003-05-23 2003-05-23 The ito film treated by nitrogen plasma and the organic luminescent device using the same

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